JP2002371245A - Coating agent for ultraviolet-cutting gas barrier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent which, when applied to a substrate, can exhibit characteristics such as gas barrier properties, ultraviolet-cutting properties, adhesion to a substrate, clarity, and flexibility. SOLUTION: This coating agent for an ultraviolet-cutting gas barrier contains (I) an organic polymer compound having amino groups, (II) an organic compound having an amino-reactive functional group and an SiOR<1> group (wherein R<1> is H or a 1-4C alkyl), (III) an organosilicon compound represented by R<2> m Si(OR<3> )n (wherein R<2> is a 1-4C alkyl optionally having an amino-nonreactive functional group; R<3> is H or a 1-4C alkyl; and n is an integer of 1 or higher provided m+n=4) and/or its hydrolyzate condensate, (IV) an organotitanium compound represented by Ti(OR<4> )4 (wherein R<4> is a 1-6C alkyl) and/or its hydrolyzate condensate, and (V) a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coating agent for ultraviolet ray cut gas barrier and a coated molded article.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide, water vapor and the like in the field of packaging materials and the like. Further, the demand for ultraviolet ray cut materials having extremely low transmittance of ultraviolet rays is increasing in the field of food packaging materials such as fried foods such as potato chips and alcoholic beverages such as alcoholic beverages which change their taste when exposed to ultraviolet light. . In packaging materials such as beverages and food containers, in order to impart gas barrier properties to molded materials such as plastic films or sheets, ethylene-vinyl alcohol copolymers,
Forming molded articles with gas barrier materials such as vinylidene chloride copolymers and aromatic nylons, laminating or coating these gas barrier materials with other materials, and aluminum foil with gas barrier properties (and UV-cutting properties) Is laminated on a film-like material, or a metal oxide that exhibits a gas barrier property (and an ultraviolet cut property) is formed by forming a vapor-deposited film.

However, among these gas-barrier materials, ethylene-vinyl alcohol copolymers and aromatic nylons are inferior in moisture resistance, and have a problem that gas barrier properties are greatly reduced as the humidity of the atmosphere increases. Since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. Also, in the above aluminum foil laminated film, the packaged contents cannot be seen from the outside, and the metal oxide vapor-deposited film is inferior in flexibility, so it is difficult to apply it to food packaging materials, and cracks are formed in the vapor-deposited layer. There is a problem in that it is likely to occur and causes a decrease in gas barrier properties.

[0004] As a molded material such as a plastic film or a sheet having the above-mentioned gas barrier properties and further having an ultraviolet cut property, the above-mentioned aluminum vapor-deposited or aluminum foil-laminated film or metal oxide-deposited film is often used. However, as described above, the packaged contents cannot be seen from the outside or are inferior in flexibility, so it is difficult to apply to food packaging materials, and there is a problem of causing a decrease in gas barrier properties and ultraviolet cut properties. there were.

In general, ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate),
Molded articles (processed products) made of various plastics such as polystyrene, PP (polypropylene), PC (polycarbonate), and acrylic resin are also more susceptible to deterioration such as yellowing when exposed to ultraviolet rays than glass substrates. Therefore,
Conventionally, ultraviolet light deterioration has been prevented by laminating a weather-resistant resin film on the surface of these plastic molded products.

[0006] However, even when the above-mentioned laminating resin film is exposed to ultraviolet rays, its progress is slightly delayed, but deterioration such as yellowing remains unchanged, and its weather resistance is insufficient. . That is, the resin film for lamination has a problem that the protective effect of the underlayer and the effect of preventing yellowing are poor and the weather resistance is poor.

Therefore, for example, Japanese Patent Laid-Open Publication No.
Japanese Patent Application Laid-Open Publication No. H11-216, proposes that a weather resistance is imparted to the above-mentioned molded body by using a fluororesin composition obtained by copolymerizing a benzotriazole-based ultraviolet absorbing monomer and a fluorine-containing monomer. ing. However, the fluororesin composition is inferior in adhesion and adhesion to a molded article such as a plastic substrate. Further, the fluororesin composition has a problem that it is expensive and is easily stained (easily stained).

[0008]

In addition, for foods and beverages in which such films or sheets having gas barrier properties and ultraviolet cut properties are used for containers, packaging materials, etc., the consumer needs to purchase the products. There are strict checks, such as poor adhesion to the plastic film of the base material and problems with the flexibility, peeling, transparency problems, and poor printing. Regardless of the quality of the product itself, it remains unsold without being purchased,
The requirements for food packaging materials used for food and beverage containers and packaging materials are extremely strict. High performance is required for transparency, flexibility, flexibility, printability, weather resistance, gloss, moisture resistance, water resistance, solvent resistance, etc., and UV can provide a new material that combines these various properties. There is an urgent need to develop a cut gas barrier coating agent and a coated molded article using the same.

Accordingly, an object of the present invention is to provide, in view of the above prior art, excellent gas barrier properties and ultraviolet cut properties, as well as excellent adhesion to substrates and the like, transparency and flexibility. To provide a novel coating agent for an ultraviolet cut gas barrier that can always stably express the above, and a coated molded article using the same.

Further, in addition to the above-mentioned objects, the present invention provides weather resistance, gloss, moisture resistance, water resistance, solvent resistance, mechanical strength, It is intended to provide a novel ultraviolet cut gas barrier coating agent capable of constantly stably expressing properties such as durability, impact resistance, heat resistance, light resistance, and printability, and a coated molded article using the same. .

[0011]

In order to solve the above-mentioned problems, the present inventors have made intensive studies on a coating agent for UV-cut gas barrier and a coated molded product. A component that effectively develops UV-cutting properties in a film-formed state,
Excellent while maintaining a component exhibiting high gas barrier properties, the above-mentioned gas barrier properties (achieved mainly by a dense molecular structure made of silica, but tend to decrease flexibility) and an ultraviolet cut. Based on these findings, we have found components that can exhibit properties such as flexibility, adhesion to substrates, etc., and transparency. The coated molded body that covers the material can meet the strict requirements of food packaging materials, etc., has excellent visibility, and the quality of the contents (taste, aroma, color, etc.)
Have been found, and the present invention has been completed.

That is, an object of the present invention is to provide (1) an organic polymer compound (I) having an amino group, a functional group capable of reacting with the amino group and a SiOR ¹ group (R ¹ is a hydrogen atom or a carbon atom And an organic compound (II) having a compound represented by the following general formula (1):

[0013]

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(Where R ² is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group, and R ³ is a hydrogen atom or a 1 And n is an integer of 1 or more and m + n = 4), and an organic silicon compound (III) represented by the following general formula (2):

[0015]

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(Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms) (IV)
And / or a hydrolysis-condensation product thereof and a solvent (V).

Another object of the present invention is to provide (2) a coating for an ultraviolet cut gas barrier, characterized by having a coating layer coated on the substrate with the coating agent for an ultraviolet cut gas barrier according to claim 1. Achieved by moldings.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The ultraviolet ray blocking gas barrier coating agent of the present invention comprises a silicon compound (I) having an amino group, a functional group capable of reacting with the amino group, and S
an organic compound (II) having an iOR ¹ group in the molecule, an organosilicon compound (III) represented by the above general formula (1) and / or a hydrolytic condensate thereof, and a compound represented by the above general formula (2) And an organic titanium compound (IV) and / or a hydrolytic condensate thereof, and a solvent (V).

With the coating agent for an ultraviolet cut gas barrier containing the above-mentioned components, it is applied and formed into a film,
Effectively and effectively, it can stably exhibit high gas barrier properties and UV cut properties, and furthermore, adhesion to substrates, flexibility, transparency, weather resistance, moisture resistance, water resistance, and solvent resistance. It can exhibit properties, mechanical strength, durability, impact resistance, heat resistance, light resistance, printability, and the like.

Hereinafter, the present invention will be described in detail.

Among these, the organic polymer compound (I) having an amino group, which is one of the main constituent components of the coating agent for ultraviolet cut gas barrier, is not particularly limited, but is preferably a polyalkylene. Immin. This is because the organic polymer compound (I) has flexibility in a coating layer obtained by coating the coating agent on a substrate (hereinafter, also simply referred to as a coating layer for an ultraviolet cut gas barrier), Polyethyleneimine is more preferable because it is used for the purpose of imparting adhesion to the composition and the like and easy film formation.

Examples of the organic polymer compound (I) having an amino group include polyalkylenimines, polyallylamines, homopolymers of amino group-containing (meth) acrylates, and amino group-containing (meth) acrylates. )
Copolymers of acrylates with other (meth) acrylates or (meth) acrylic acid, cation exchange resins, and the like. Among them, polyalkylene imines are preferable, and polyethylene imine is particularly preferable, from the viewpoints of transparency and hot water resistance of the coating layer for ultraviolet cut gas barrier.

The polyalkyleneimines mentioned above include, for example, Epomin series manufactured by Nippon Shokubai Co., Ltd .; Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin SP-
018, Epomin SP-103, Epomin SP-11
And polyethyleneimine such as Epomin SP-200, Epomin SP-300, Epomin SP-1000, and Epomin SP-1020 (all of which are trade names), but it is needless to say that these should not be limited to these. No.

The above-mentioned polyallylamines include
For example, PA that is already commercially available from Nitto Boseki Co., Ltd.
Examples thereof include, but are not limited to, AL and PAA-H (all of which are trade names).

Examples of the amino group-containing (meth) acrylate include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

Examples of the other (meth) acrylates include a monomer copolymerizable with an amino group-containing (meth) acrylate and a polymer compound copolymerized with an amino group-containing (meth) acrylate. It may be.

The number average molecular weight of the organic polymer compound (I) is in the range of 250 to 200,000, preferably 250 to 100,000, more preferably 300 to 10,000. When the number average molecular weight is less than 250, the flexibility of the UV cut gas barrier coating layer formed is poor, or the surface of a base material (including the base material and other coating layers formed on the substrate). While inferior in film-forming properties when coating on top,
If the molecular weight is larger than 200,000, the formed ultraviolet cut gas barrier coating layer may be poor in transparency and the flexibility of the ultraviolet cut gas barrier coating layer may be poor.
However, among the organic polymer compounds (I) that can be used in the present invention, those having a complex structure that cannot be measured by the number average molecular weight specified above are included, and the number average molecular weight specified here is included. Does not exclude these from the present invention.

Further, as another one of the main components of the coating agent for an ultraviolet cut gas barrier according to the present invention, a functional group capable of reacting with an amino group and a SiOR ¹ group (R ¹ is a hydrogen atom or a carbon atom having 1 to 4 carbon atoms) Which represents an alkyl group of the formula (1) in the molecule. By having a SiOR ¹ group in the molecule, hydrolysis or condensation proceeds before or after the reaction with the organic polymer compound (I) having an amino group, and the organosilicon compound (III) or the organotitanium compound (IV) Because condensation polymerization proceeds by causing co-hydrolytic condensation with the hydrolyzable condensed group of, it is possible to quickly form a dense film,
Excellent adhesion to base materials, etc., and 20 ° C after boiling sterilization
Excellent gas barrier properties, such as being able to maintain high gas barrier properties even under a high humidity of 90% Rh, and being excellent in target gas barrier properties, ultraviolet cut properties, and adhesion to substrates and the like. It has an advantage particularly effective in forming a coating layer for an ultraviolet cut gas barrier.

Here, the functional group capable of reacting with the amino group is not particularly restricted but includes, for example, an epoxy group, a carboxyl group, an isocyanate group, a thioisocyanate group, an oxazolinyl group, a (meth) acryl group, Examples include an aldehyde group, a ketone group, and an alkyl halide group. Preferably, ease of reaction with an amino group,
It is an epoxy group from the viewpoint of hot water resistance.

R ¹ in the above SiOR ¹ group is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, the alkyl group having 1 to 4 carbon atoms is not particularly limited, and a methyl group, an ethyl group, a propyl group, a linear alkyl group such as a butyl group, a branched alkyl group such as an isopropyl group,
Any of a cyclic (alicyclic) alkyl group such as a cyclopropyl group or a cyclobutyl group may be used. R ¹ is preferably a methyl group or an ethyl group from the viewpoints of excellent hydrolytic condensation reactivity, advantages in forming a dense film, and ease of reaction.

As described above, a functional group capable of reacting with an amino group and a SiOR ¹ group (R ¹ is a hydrogen atom or
Represents an alkyl group of 4 to 4. ) In the molecule is not particularly limited, but specifically, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4
-Epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysisilane, γ-glycid A silane coupling agent having an epoxy group such as xypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane and a Si (OR ¹ ) group (R ¹ has the same meaning as described above) (hereinafter simply referred to as an epoxy group-containing silane) Γ-isocyanopropyltrimethoxysilane, γ
Silane coupling containing an isocyanate group such as isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane, γ-isocyanopropylmethyldiethoxysilane and a Si (OR ¹ ) group (R ¹ has the same meaning as described above) Agents (hereinafter sometimes abbreviated simply as an isocyanate group-containing silane coupling agent) and the like, and one or more of these can be used.

Further, as another one of the main constituent components of the coating agent for ultraviolet ray cut gas barrier of the present invention, general formula (1): R ² _m Si (OR ³ ) _n (where R ² is An alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group; R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; And m + n = 4.)
And / or a hydrolyzed condensate thereof. When the coating agent for ultraviolet ray cut gas barrier contains an organosilicon compound (III) and / or a hydrolyzed condensate thereof, the adhesion to a substrate or the like, the hard coat property, and the heat resistance are improved, and the packaging of foods and beverages is performed. Boiling sterilization which can be said to be unavoidable when used as a material, and then under a severe storage environment (for example, at a high humidity of about 20% 90% Rh).
This is preferable because a sufficiently high gas barrier property can be maintained. This organosilicon compound (III)
Can be distinguished from the organic compound (II) having an SiOR ¹ group in that it has no functional group capable of reacting with the functional group (amino group) of the organic polymer compound (I).

R ² in the above general formula (1) has 1 to 1 carbon atoms.
Any alkyl group having 1 to 4 carbon atoms having a functional group that does not react with an alkyl group of 4 or an amino group may be used. here,
The functional group that does not react with the amino group is not particularly limited, and includes, for example, an amino group and a vinyl group. The alkyl group having 1 to 4 carbon atoms is not particularly limited, and may be a methyl group, an ethyl group, a propyl group, a linear alkyl group such as a butyl group, a branched chain alkyl group such as an isopropyl group, a cyclopropyl group, Any of a cyclo (alicyclic) alkyl group of a cyclobutyl group may be used, but it is preferably excellent in the reactivity of hydrolytic condensation, advantageous in forming a dense film, and from the viewpoint of ease of reaction. These are a methyl group and an ethyl group. Therefore, R ² is preferably an alkyl group having 1 to 4 carbon atoms having a vinyl group from the viewpoint of heat resistance and boiling resistance. When m is 2 or more, R ² may be the same or different.

R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is not particularly limited, and may be a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a branched chain alkyl group such as an isopropyl group, a cyclopropyl group, or a cyclobutyl group. May be any of the cyclic (alicyclic) alkyl groups. R ³ is preferably a methyl group or an ethyl group from the viewpoint of excellent hydrolytic condensation reactivity and the advantage of forming a dense film. Note that R ³
May be the same or different when n is 2 or more.

In the general formula (1), n is an integer of 1 or more, m is an integer of 0 or more, and m + n = 4. From the viewpoints of heat resistance, boiling resistance, and water resistance of the coating layer for ultraviolet cut gas barrier obtained by coating the coating agent for ultraviolet cut gas barrier, m = 0 and n =
It is preferably 4.

Specific examples of the organosilicon compound (III) represented by the general formula (1) described above include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi Isopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane,
Diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltri Alkoxysilanes such as ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, methyltriacetoxysilane, trimethylsilanol, and the like, or high-molecular-weight organic compounds containing these compounds. , One or more of these can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferred from the viewpoints of reactivity and good boiling resistance, moisture resistance and water resistance of the coating layer for ultraviolet cut gas barrier.

The reason why the organic silicon compound (III) represented by the above general formula (1) may contain a hydrolyzed condensate is that the organic compound (II) and the organic silicon compound (III) ( And organic titanium compounds (IV))
This is because it is preferable to carry out hydrolysis and condensation in advance in order to prevent drying when forming the coating layer for ultraviolet cut gas barrier. In other words, it is preferable that these hydrolysis-condensation products be present in the coating material for ultraviolet ray cut gas barrier. These (co) hydrolytic condensation reactions proceed with moisture in the air, but can be performed efficiently using a known catalyst such as an acid or a base. The hydrolysis reaction is preferably performed in a solvent, and the coating agent for an ultraviolet cut gas barrier containing such a solvent also facilitates the coating operation on a substrate (or another coating layer or an adhesive layer).

Further, as another one of the main constituent components of the coating agent for ultraviolet ray cut gas barrier of the present invention, general formula (2): Ti (OR ⁴ ) ₄ (wherein R
⁴ is an alkyl group having 1 to 6 carbon atoms. ) And / or a hydrolytic condensate thereof. When the coating agent for ultraviolet ray cut gas barrier contains an organic titanium compound (IV) and / or a hydrolyzed condensate thereof, the coating layer obtained by coating the coating agent has TiO—Ti
O-SiO-SiO structure (so-called block structure) or T
An iO-SiO-TiO-SiO structure (a so-called random structure) is formed. Among them, the block structure is particularly effective in cutting ultraviolet light, that is, sufficient ultraviolet light cutting for the entire ultraviolet wavelength range of 350 to 400 nm. This is preferable because the film can exhibit properties and can maintain film strength.

Here, R ⁴ in the general formula (2) is an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is not particularly limited, and may be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a linear alkyl group such as an n-hexyl group, Isopropyl group, isobutyl group, sec-butyl group, tert-
Butyl group, isopentyl group, neopentyl group, 1,2-
Dimethylpropyl group, 1,3-dimethylbutyl group, 1-
It may be any of a branched alkyl group such as an isopropylpropyl group and a 1,2-dimethylbutyl group, and a cyclic (alicyclic) alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. R ⁴ is preferably an n-butyl group from the viewpoint of excellent hydrolytic condensation reactivity and the advantage of forming a dense film. The four R ⁴ in the general formula (2) may be the same or different, but from the viewpoint of ease of reaction, it is preferable that all four are the same.

Specific examples of the organotitanium compound (IV) represented by the above general formula (2) include, for example, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium Titanium, tetrahexyloxytitanium and the like can be mentioned, and one or more of these can be used. Above all, tetrabutoxytitanium is preferred from the viewpoint of reactivity and that the coating layer obtained by coating shows good transparency.

The organic titanium compound (IV) represented by the above general formula (2) may contain a hydrolyzed condensate, because the organic compound (II), the organic silicon compound (III) and This is because the organic titanium compound (IV) is preferably subjected to hydrolysis-condensation in advance in order to prevent drying when forming the ultraviolet cut gas barrier coating layer. In other words, it is preferable that these hydrolysis-condensation products be present in the coating material for ultraviolet ray cut gas barrier. These (co) hydrolytic condensation reactions proceed with moisture in the air, but can be performed efficiently using a known catalyst such as an acid or a base.
Further, the hydrolysis reaction is preferably performed in a solvent (V), and the coating agent for an ultraviolet cut gas barrier containing the solvent (V) is coated on a substrate (or another coating layer or an adhesive layer). Work is also easy.

The ultraviolet ray blocking gas barrier coating agent of the present invention contains a solvent (V) which can suitably dissolve (or disperse) the above-mentioned main components and the like. Examples of the solvent solvent (V) include the above-mentioned organic polymer compound (I), organic compound (II), organic silicon compound (III) and / or hydrolyzed condensate thereof, organic titanium compound (IV) and / or hydrolyzate thereof. Decomposition condensate,
There is no particular limitation as long as it can dissolve various additives used as necessary. Examples thereof include methanol, ethanol, 2-propanol, butanol, pentanol, ethylene glycol, diethylene glycol, and triethylene glycol. Alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and triethylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, benzene and xylene; hexane and heptane , Octane and other hydrocarbons; methyl acetate, ethyl acetate, propyl acetate, butyl acetate and other acetates; Ether, propyl ether, tetrahydrofuran, water and the like Ageraru. These may be used alone or as a mixture of two or more. Among them, alcohols such as methanol and ethanol are preferred because they are excellent in stability during hydrolysis reaction and storage stability. In particular, in the present invention, the cross-linking of the obtained coating layer becomes dense and suitable according to the type of the component other than the solvent (V) in the ultraviolet ray blocking gas barrier coating agent among these. It is desirable to appropriately select an appropriate solvent so that it has flexibility and can effectively exhibit various properties such as desired gas barrier properties and ultraviolet cut properties.

Further, the coating agent for an ultraviolet cut gas barrier of the present invention may contain various inorganic or organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent and a thickener, if necessary. Can be added in an appropriate amount.

Next, the compounding amount of the above-mentioned organic polymer compound (I) depends on the amount of the organic compound (II) and the amount of the organic silicon compound (II).
Since it differs depending on the compounding ratio of I) and / or its hydrolyzed condensate, the organotitanium compound (IV) and / or its hydrolyzed condensate, and whether or not other additives are used, it is not necessary to uniquely define it. Although it is not possible, the constituents of the above coating agent for UV cut gas barrier (however,
Solvent (V)), usually 10 to 10
It is in the range of 90% by weight, preferably 20-80% by weight. The amount of the organic polymer compound (I) is 10% by mass.
If it is less than 1, the film-forming properties of the coating layer for ultraviolet cut gas barrier may be inferior. On the other hand, if it exceeds 90% by mass, the flexibility and water resistance of the coating layer for ultraviolet cut gas barrier may be poor.

The compounding amounts of the organic compound (II) are as follows: the organic polymer compound (I), the organosilicon compound (III) and / or its hydrolytic condensate, and the organic titanium compound (IV) and / or its hydrolyzate. Although it cannot be unambiguously specified because it differs depending on the compounding ratio of the decomposition condensate and whether or not other additives are used, the components of the coating agent for the ultraviolet ray cut gas barrier (excluding the solvent (V)) ), Usually 5 to 50
%, Preferably in the range of 7 to 15% by weight. When the amount of the organic compound (II) is less than 5% by mass,
The flexibility of the coating layer for ultraviolet cut gas barrier may be poor. On the other hand, if it exceeds 50% by mass, the water resistance of the coating layer for ultraviolet cut gas barrier may be poor.

The amounts of the organosilicon compound (III) and / or the hydrolytic condensate thereof are determined according to the amounts of the organic polymer compound (I), the organic compound (II) and the organic titanium compound (I
V) and / or its hydrolysis-condensation product cannot be unambiguously defined because it differs depending on the compounding ratio of the hydrolysis-condensation product and the use of other additives. , Except for the solvent (V)), usually 10 to 80
%, Preferably in the range of 30 to 70% by weight. When the amount of the organosilicon compound (III) and / or the hydrolyzed condensate thereof is more than 80% by mass, the flexibility of the coating layer for ultraviolet cut gas barrier may be poor. On the other hand, if it is less than 10% by mass, the water resistance of the coating layer for ultraviolet cut gas barrier may be poor.

The compounding amount of the above-mentioned organic titanium compound (IV) and / or its hydrolytic condensate is determined according to the above-mentioned organic polymer compound (I), organic compound (II), and organosilicon compound (III) and / or its hydrolyzate. Although it cannot be unambiguously specified because it differs depending on the compounding ratio of the decomposition condensate and whether or not other additives are used, the components of the coating agent for the ultraviolet ray cut gas barrier (excluding the solvent (V)) ) Is usually 0.5 to
The range is 5% by mass, preferably 1 to 3% by mass. When the amount of the organotitanium compound (IV) and / or its hydrolytic condensate exceeds 5% by mass, the transparency of the coating layer for ultraviolet cut gas barrier obtained by coating the coating agent on a substrate May be inferior. On the other hand, 0.5
When the amount is less than mass%, the ultraviolet cut of the coating layer for an ultraviolet cut gas barrier obtained by coating the coating agent on a substrate may be inferior.

The blending amount of the solvent (V) is not particularly limited, but is usually 50% based on the total mass of the ultraviolet ray cut gas barrier coating agent (here, including the solvent (V)) as 100% by mass. ~ 97 mass%, preferably 7
It is in the range of 0 to 90% by mass. The amount of the solvent (V) is 5
When the amount is less than 0% by mass, the reaction stability of the UV cut gas barrier coating agent may be inferior, and the viscosity of the UV cut gas barrier coating agent may increase during coating and uniform coating may be performed. May be gone. On the other hand, when the content exceeds 97% by mass, the productivity in forming the coating layer for ultraviolet cut gas barrier may be inferior, and the concentration of the active ingredient may be too low. In some cases, the thickness cannot be secured.

The organic polymer compound (I), the organic compound (II), the organosilicon compound (III) and / or a hydrolytic condensate thereof, the organic titanium compound (IV) and / or a hydrolytic condensate thereof, The amount of various inorganic or organic additives other than the solvent (V), such as a curing catalyst other than the solvent (V), a wettability improver, a plasticizer, an antifoaming agent, and a thickener, is not included in such additives. The organic polymer compound (I), the organic compound (II), the organic silicon compound (III) and / or a hydrolyzed condensate thereof, the organic titanium compound (IV) and / or a hydrolyzate thereof can sufficiently exhibit various properties. The decomposition condensate and the solvent (V) are not particularly limited as long as they do not affect the effects of the present invention such as the gas barrier property and the ultraviolet cut property of the present invention.

The above organic polymer compound (I), organic compound (II), organosilicon compound (III) and / or its hydrolytic condensate, organotitanium compound (IV) and / or its hydrolytic condensate, Furthermore, the total blending amount of the ultraviolet ray cut gas barrier coating agent including the other additives (excluding the solvent (V)) is always 100% by mass regardless of the combination.

The method for preparing the coating agent for an ultraviolet cut gas barrier according to the present invention is not particularly limited. For example, (1) the organic polymer compound (I), the organic compound (II), A compounding component containing the above-mentioned organosilicon compound (III) and / or its hydrolytic condensate, the organotitanium compound (IV) and / or its hydrolytic condensate, and the solvent (V) (including other optional components) (2) a functional group reaction between the organic polymer compound (I) and the organic compound (II) in the presence of the solvent (V) in advance, A method of simultaneously or sequentially adding the silicon compound (III) and / or its hydrolytic condensate and the organic titanium compound (IV) and / or its hydrolytic condensate,
(3) In the presence of the organic compound (II) and the solvent (V), the organic polymer compound (I) and the organic silicon compound (III), and the organic polymer compound (I) and the organic titanium compound (IV) ) Are simultaneously or sequentially (co) hydrolyzed and condensed, and (4) the organic polymer compound (I) and the organosilicon compound (II) in the presence of the solvent (V).
I) and a method in which the organic polymer compound (I) and the organic titanium compound (IV) are simultaneously or sequentially cohydrolyzed and condensed, and then reacted with the organic compound (II). They should not be restricted at all. It is preferable that the solvent (V) is appropriately replenished or supplemented with a suitable amount of a suitable type at an appropriate time according to the preparation step or method.

Next, the coated molded article for an ultraviolet cut gas barrier of the present invention is characterized in that it has a coating layer coated on the substrate with the above-mentioned coating composition for an ultraviolet cut gas barrier.

Examples of the substrate that can be used in the ultraviolet-cut gas barrier coating molded article of the present invention include various applications that require ultraviolet cut properties and gas barrier properties,
For example, a plastic base material used for a container or a packaging material of a food or a beverage can be used. Specifically, since the required properties required for the base material differ for each of these uses, it cannot be uniquely defined, and according to each required property (for example, mechanical properties, optical properties, etc.), The optimum base material should be appropriately selected, and is not particularly limited.

Examples of the substrate include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene isophthalate, and the like.
Polyester resins such as polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof, polyamides, polystyrene, ABS resin, poly (meth) acrylate, polyacrylonitrile,
Thermoplastic resins such as polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide, polysulfone, polyetherketone, ionomer resin, and fluororesin, melamine resin, polyurethane resin, epoxy resin, phenolic resin, unsaturated polyester resin, Thermosetting resin such as urea resin, alkyd resin, silicon resin,
Composite materials such as fiber reinforced plastic (FRP) and the like can be mentioned. As described above, suitable base materials are different for each application. For example, when used for food and beverage containers and packaging materials, mechanical strength, transparency, heat resistance (boiling resistance) Polycarbonate (PC), high-impact polystyrene (HIPS), polyethylene terephthalate (PET), ethylene vinyl alcohol copolymer (E)
VOH), gas barrier resins, polyolefin-based resins such as polyethylene and polypropylene, polyacrylonitrile, polyamide, and cellophane are preferred, and thermoplastic resins such as polypropylene, polyamide, and PET are particularly preferred because of their ease of processing and versatility. Is more preferred. These may be used alone or in combination of two or more. In addition, these base materials themselves may be formed into a multilayer structure with materials having different properties in order to obtain required characteristics that cannot be obtained with a single material. In the present invention, the use of a plastic substrate having transparency as described above is the most common, but a translucent or opaque plastic substrate, and further, such as glass, ceramics, metal foil and metal oxide. Application (including the case where it is applied to a part by vapor deposition etc.)
Does not exclude.

The shape of the substrate is not particularly limited, and has a characteristic that it can be formed into an arbitrary shape, and can be appropriately selected according to the intended use. Therefore, the coating product for ultraviolet cut gas barrier of the present invention obtained by forming the coating layer for ultraviolet cut gas barrier on such a substrate is not to be limited by its name, for example, food and beverage products Any form used for containers and packaging materials should be included in the scope of the present invention. Examples of the shape of the base material include not only a film shape but also a sheet shape, a molded shape such as a bottle shape (including a PET bottle) or a tray shape, a bag shape obtained by secondary processing of a film or the like, and the like. There may be. Further, it may be a film or sheet, or may have a curved surface.

Since the thickness of the above-mentioned base material varies depending on the intended use, it is difficult to uniquely define the thickness, and it should be appropriately selected according to the intended use. For example, when used for food and beverage containers and packaging materials, usually 7 ~ 100μ
m, preferably in the range of 10 to 30 μm. When the thickness of the film substrate is less than 7 μm, it is not preferable because pinholes are generated and mechanical strength is insufficient. On the other hand, when the thickness exceeds 100 μm, the productivity of the coated molded article is inferior, and it is difficult to satisfy the demand for thinner films required for containers and packaging materials.

In the case where a transparent plastic substrate or the like is used as the substrate, for example, its surface is subjected to plasma treatment or corona discharge treatment in advance, or the substrate surface is treated in an atmosphere containing oxygen in an atmosphere containing oxygen. It is preferable to form the coating layer after irradiating ultraviolet rays having a wavelength of about 400 nm.

Further, depending on the state of adhesion of the dirt on the substrate (substrate), if the coating cannot be performed uniformly by repelling the coating agent for ultraviolet cut gas barrier, etc., cleaning or surface modification of the substrate surface is required. Can improve it. Methods of cleaning and surface modification include degreasing cleaning with an organic solvent such as alcohol, acetone, and hexane, cleaning with an alkali or acid, polishing the surface with an abrasive, cleaning methods such as ultrasonic cleaning, and ultraviolet irradiation treatment. And surface modification methods such as ultraviolet ozone treatment, plasma treatment, corona discharge treatment, and heat treatment.

Further, the coating product for ultraviolet ray cut gas barrier of the present invention has a coating layer (ultraviolet ray cut gas barrier coating layer) coated on the above-mentioned substrate with the above ultraviolet ray cut gas barrier coating agent. . Here, the UV cut gas barrier coating layer may be formed directly on the base material, or may be indirectly formed via another coating layer (including an adhesive layer, a decorative layer, etc.) other than the UV cut gas barrier coating layer. May be formed.

The method of coating the coating agent for ultraviolet cut gas barrier on the surface of a substrate or another coating layer or the like (hereinafter, also simply referred to as a substrate or the like) should be particularly limited. Rather, it is possible to appropriately use a conventionally known thin film forming technique or coating technique, such as a roll coating method, a dip coating method, a bar coating method, a nozzle coating method, a die coating method, and a spraying method. Various printing methods such as a coating method, a spin coating method, a curtain coating method, a flow coating method, screen printing, gravure printing, and curved surface printing, or a combination thereof can be employed. Among them, the die coating method is preferable in terms of increasing the stability of the coating agent for ultraviolet cut gas barrier.

After coating with the above-mentioned UV cut gas barrier coating agent, the UV cut gas barrier coating layer formed on the substrate is cured and dried.
In such curing and drying, heating or heating and humidification is preferable in that a dense ultraviolet cut gas barrier coating layer having excellent hard coat properties can be quickly formed. When heating here, it is preferable to heat at a temperature lower than the heat-resistant temperature of the substrate or other coating layers.
From the viewpoint of preventing evaporation of the organosilicon compound (III) and the organotitanium compound (IV) during drying, the hydrolysis condensate of the organosilicon compound (III) and the hydrolysis of the organotitanium compound (IV) are used. It is preferable to use the above-mentioned coating agent for an ultraviolet cut gas barrier prepared by mixing a condensate.

[0062] Further SiOR ¹ groups of the organic compounds of unreacted coating layer for UV gas barrier (II), an organosilicon compound SiOR ³ groups of (III), reducing the TiOR ⁴ group of the organic titanium compound (IV) It is desirable to maintain sufficient gas barrier properties even under a high-temperature and high-humidity environment, in order to maintain UV-cutting properties.After coating the UV-cutting gas barrier coating agent on a surface of a substrate or the like by an appropriate coating method, The UV cut gas barrier coating layer is cured and dried, and thereafter, the unreacted SiOR ¹ group of the organic compound (II) and the SiOR ³ group of the organic silicon compound (III) in the UV cut gas barrier coating layer. organotitanium compound is preferably a TiOR ⁴ group be aged reacting (condensation) (aging) treatment of (IV), for example, the upper After coating and drying a coating agent for UV gas barrier on the surface of the substrate such as an effective heat treatment in reducing the unreacted group (e.g., 40-60
(A heat treatment at a temperature between 1 DEG C. for 1 to 7 days) and a method of performing corona treatment. However, the aging treatment may be performed immediately after the above-mentioned UV-cut gas barrier coating agent is applied on the surface of a substrate or the like and dried and cured to form a UV-cut gas barrier coating layer. The coating may be performed after a gas barrier coating agent is applied on the surface of a substrate or the like, dried and cured to form a UV-cut gas barrier coating layer, and then another coating layer is formed. Here, the heat-resistant temperature of the base material or the like is substantially the upper limit temperature at which the properties of the base material or the like can be maintained, and for a glass base material, for example, the softening point or the devitrification temperature (normally 600 to 700 ° C.) ), For example, a glass transition point, a crystallization temperature, a decomposition point, and the like. It is needless to say that before the coating of the ultraviolet ray cut gas barrier coating agent, another coating layer or an adhesive layer such as a known anchor coat layer such as a urethane resin may be provided on the surface of the substrate or the like. Nor.

By the above curing, drying, and aging treatments, a desired coating layer for an ultraviolet cut gas barrier can be formed on the surface of a substrate or the like. The thickness of the dried layer of the ultraviolet light blocking gas barrier after drying cannot be uniquely defined because it varies depending on the intended use.
Any material can be used as long as it can exhibit high gas barrier properties, ultraviolet cut properties, and further exhibit properties such as adhesion to a substrate and the like, transparency, flexibility, and moisture resistance.
It is in the range of 5 μm, preferably 0.5-3 μm. When the thickness of the coating layer for ultraviolet ray cut gas barrier after drying is less than 0.1 μm, the coating is not uniform, and the gas barrier property, ultraviolet ray cut off property, adhesion to a substrate, etc., transparency, flexibility, etc. And properties such as moisture resistance are not sufficiently developed. On the other hand, when the thickness after drying of the coating layer for ultraviolet cut gas barrier exceeds 5 μm, cracks are easily generated in the coating.

In the coating layer for UV-cut gas barrier obtained by coating the above-mentioned UV-cut gas barrier coating agent on a substrate, the same type (composition) of the above-mentioned UV-cut gas barrier coating agent is coated on the substrate. The coating (application) may be divided into several layers, or the above-mentioned coating agents for ultraviolet ray cut gas barriers of different types (compositions) may be separately coated (applied) to form a multilayer having a different composition and thickness for each layer. An ultraviolet cut gas barrier coating layer having a structure (another coating layer may be formed on the way) may be formed.

As described above, the ultraviolet-cut gas barrier coating molded article of the present invention is excellent in gas barrier properties and ultraviolet cut properties, and is also excellent in adhesion to substrates and the like, transparency and flexibility. Characteristic can always be stably expressed. Among these properties, regarding gas barrier properties, the required standards differ depending on the intended use, and also differ depending on the type of base material and the overall laminated structure. For example, when used as a container or packaging film for foods and beverages such as potato chips and alcoholic beverages, which are liable to lose its flavor due to ultraviolet rays or discoloration (yellowing), it can be described in high humidity (20 ° C90
% Rh) at a gas (oxygen) permeability of 30 ml / m ² · 2
4 hrs or less, preferably 20 ml / m ² · 24 hrs
Or less, more preferably 10 ml / m ² · 24 hrs or less. The gas (oxygen) permeability is 30m
If it exceeds 1 / m ² · 24 hrs, a gas such as oxygen cannot be cut sufficiently as a molded article for ultraviolet cut gas barrier, and a considerable amount of oxygen will be transmitted. However, since the flavor of potato chips and alcoholic beverages is lost or discolored (yellowing), the shelf life of such foods and beverages (extended shelf life of high quality) cannot be sufficiently achieved. Will be.

Examples of the coated molded article for ultraviolet cut gas barrier according to the present invention include, in particular, containers and packaging films for foods and beverages, containers for pharmaceuticals such as eye drops, infusion bags, medical Packaging materials for containers, plastic molded products such as containers, home appliances, steel products, large structures, interior and exterior parts for automobiles, building materials, wood products, glass products, and the like are included, but are not particularly limited.

[0067]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the present invention in any way, and can be modified and implemented without departing from the spirit of the preceding and the following. Everything is included in the technical scope of the present invention.

Example 1 Epomin SP-006 {polyethyleneimine: trade name of Nippon Shokubai Co., Ltd., organic polymer compound (I)} 10 g,
γ-glycidoxypropyltrimethoxysilane ｛organic compound (II) II8 g and methanol ｛solvent (V)｝ 10
After reacting 0 g of the mixture at 60 ° C. for 3 hours, the mixture was cooled to room temperature, and then mixed with 4 g of water / solvent (V) and 4 g of methanol / solvent (V).
10 g of the mixed solution was added and reacted for 30 minutes. Further, 40 g of M silicate 51 (tetramethoxysilane oligomer: a hydrolytic condensate of organosilicon compound (III) manufactured by Tama Chemical Co., Ltd.) and 220 g of methanol / solvent (V) / 220 g Was added and reacted for 1 hour. 0.5 g of tetrabutoxytitanium {organotitanium compound (IV)}
A mixed solution of -propanol {solvent (V)} (20 g) was added to obtain a coating agent (1) for an ultraviolet cut gas barrier.

This UV-cut gas barrier coating agent (1) was applied to a 25 μm-thick PET film (substrate) so that the thickness after drying became 1 μm, dried at 100 ° C. for 20 seconds, and further dried at 60 ° C. Aged for 5 hours, coated with UV-cut gas barrier coating on PET film substrate (1)
I got

Table 1 below shows the characteristic evaluation of the coating product (1) for a UV cut gas barrier.

Comparative Example 1 The procedure of Example 1 was repeated, except that tetrabutoxytitanium (organotitanium compound (IV)) was not added.
A comparative coating agent (1) and a comparative coated molded article (1) were obtained.

The characteristics of the comparative coated molded article (1) are also shown in Table 1 below.

[0073]

[Table 1]

Light transmittance (%) in Table 1: Light transmittance at 360 nm was measured.

Oxygen permeability in Table 1: Measured at 20 ° C. and 90% Rh using an oxygen permeability measuring device manufactured by Modern Controls. The unit is ml / m ² · 24 hrs · atm.

Flexibility in Table 1: Determined by the following tests.

：: The molded article was bent at 180 ° and no crack was generated.

×: Cracks occur when the molded body is bent at 180 °.

[0079]

As described above, the coating agent for a UV-blocking gas barrier of the present invention and the coating product for a UV-shielding gas barrier having a coating layer formed by coating the coating agent on a substrate are provided by the coating agent. When coated on a substrate, excellent UV-cutting properties, gas barrier properties, adhesion to substrates, etc., transparency, flexibility, weather resistance, gloss, moisture resistance, water resistance, solvent resistance, Mechanical strength,
Since it can exhibit properties such as durability, impact resistance, heat resistance, light resistance, flexibility, and printability, it can be widely applied in various fields where (part of) these properties are required. Yes, for example, those having excellent oxygen barrier properties with low oxygen permeability can be applied to the food packaging field, and those having excellent carbon dioxide gas permeability with low carbon dioxide permeability are used for containers such as soft drinks and beer. For example, it can be applied to containers and packaging materials of various foods and beverages. In particular, containers and packaging materials for foods and beverages such as fried foods such as potato chips and alcoholic beverages that are easily oxidized and lose their flavor due to ultraviolet light and discoloration (yellowing) (specifically, plastic bases) It can be applied to a food packaging film or a PET bottle container in which an ultraviolet cut gas barrier coating layer is formed on a material. Furthermore, electronic components used for liquid crystal display devices, portable terminals or mobile devices (for example, polymer film substrates having a UV blocking coating layer of a liquid crystal display, a gas barrier coating layer formed thereon), medical equipment / apparatus, and pharmaceuticals (For example, a blood storage bag or a container for eye drops). In addition, since the properties of each coating layer formed on the substrate are not impaired even when subjected to stress due to shrinkage, shrink films (shrinkable films) used in containers and packaging materials for food and beverages And can be applied in a very wide range.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 185/00 C09D 185/00 F term (Reference) 4F100 AH06B AH08B AK01A AK52B AK52K AT00A BA02 GB15 GB23 JB07 JD02 JD09 JD09B JJ03 JK06 JK10 JK17 JL09 JN01 JN08B 4J038 DJ011 GA09 JC32 JC34 JC35 JC36 JC38 NA03 NA04 NA11 NA12 NA14 NA19 PB04 PC08

Claims (2)

[Claims] An organic polymer compound (I) having an amino group, a functional group capable of reacting with the amino group and a SiOR ¹ group (R
¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) In the molecule, and an organic compound (II) having the following general formula (1): (Wherein, R ² is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group, and R ³ is a hydrogen atom or 1 to 4 carbon atoms.
N is an integer of 1 or more and m + n =
4. ) And / or a hydrolytic condensate thereof, and the following general formula (2): (Wherein, in the formula, R ⁴ is an alkyl group having 1 to 6 carbon atoms). The solvent contains (V) an organic titanium compound (IV) and / or a hydrolytic condensate thereof. Characteristic coating agent for UV cut gas barrier. 2. An ultraviolet-cut gas barrier coating molded article having a coating layer coated on the substrate with the ultraviolet-cut gas barrier coating agent of claim 1.